Acid azo dyes



Patented Sept. 30, 1952 UNITED STATES PTE'NT OFFICE 2,612,496 aomazo DYES Bela Gaspar, Beverly Hills, and Paul Daniel Dreyfuss, Van Nuys, Calif., assignors, by mesne assignmenta'to. said Gaspar No Drawing. Application April 2, 194s, Serial No. 18,713

This invention relates to dyes and more par-- ticularly' to: blue and blue-green disazodyes and whereinB is. a..monocyclic. or polycyclic. aromatic residue containing,..the, azobondslshown in, 1,4-

position, .A. istharesiduenof.naphthalene, the OH groun shcwnistandsiin.ortho,.position.to the. azo.

group .-linked. 110., saidlnaphthalene ,residue, m.v standslion-one ofthe-integersl. andn2, acyl stands.

10. Claims. (01. 26016.fl)

fertile. residue of. acarbox'ylicor. sulfhnic. acid.

and. A ,standsforgthe. rsid'ueof. anwazplconpler contaminate hydroxyl group 1112 c114 positionto theazo grbundihked .to .said-azo. coupler. I

A survey ilthe. heretofore,.,known .azo.-. dyes shows that the number of brilliant azo dyes which absorb the blue cp -the green-lightis' uite large but that there are only a very limited number of brilliant azo dyes which absorb:in the' longer wave range of the visible' spectruma Mostofthe dyes which absorb in the longer wave range are found in the group of the tris and tetralrisi-azo dy'es.-= The accumulation soi' three orfour 'azogroups in one molecule in:most cases the consequence that besides a-"shift-oft-he absorption maximum to longer wave lengthsatheabsor'p tion band is broader, that is; the dyebecomes 'dull or blackish. Azo dyes, absorbing in the red end of the spectrum and having good transmfmsion-in the blue and green-secti'ons of th-spectrumare very: rare. It is comm-en'- practice-,- therefore; to

produce green and greenish-blue-shadesby using a mixturewof, yellow and; blue. dyes... This. procedurahhoweyeulhasmany disadvantages.

Itlis remarkablethat. dyes .of the..general. fo1i-.

mulaeabove. .proye 1to.be brilliant. and stable .dyesQI Theybare .exceptionallylbright and ofwaIgreat, brilliance ,of hue, .j and. .their. absorption curves have. a .very steep.- increment... A large numberof blue-green azo dyes,, which appear.,quite-.brilliant.

in daylight, appear dull in artificia1 light, Quite differently, the dyes {of this'invention are very brilliant,- even in artificial lightw The unexpected spectral characteristics of the dyes of the general formula above supposedly are I due a: the.

presence of the resonance system where X stands for 1 or 2 andzwhere-Yis-ipart of a naphthalene nucleus;.containihggan; .acyl amino residue. It is particularly surprisingthat the disazo dyes of the, above;generallformula.ab-i sorb, in spite oftheir. comparatively simple structure, in the far redzendbf. thelvisiblei spectrum and that it isapossibla. therefore to"produce: brilliant dyes; inythis. class.;,-with..axpronounced greenish shade. As. the newdyesas. a.'class'..p'er-;- mit many possibilities of variatiomtheycanbe applied wherever 'sulfonated dyes are useful; Their afiinityfor all kindiof fibers',.their penetra-.

tive capacity in colloids,..their. fastness to diifu-:

sion in photographic colloids, their solubility,:the

accessibility to .bleachingin photographic processes, their capacity to. dye evenly, their fastness to washing andv ironing, their shade and other desirable qualities canbewvaried within wide limits by changing the number and position-0f the. sulfonic acid groupsin the. dyestufi molecule,

by modifying the acyl substituent in the-aminonaphthol residue, by -substituents in the radical B, by variations in the azo*coupler A andby.

linking two or more dye units by means of-"external bonds in a manner which willbeexplained further on.

Our new dyes are not only simpl in'their chemical structure but their methodof. preparation is equally simple. Onlya few steps arere.-- quired to transformmommonly available starting materials into, our valuable dyes, .anda purification of the dyes is unnecessary in most. casesbecause. of a striking difference in. affinityof.-.the

disazo-dyes tothe fiber compared with theby aminonaphthol. The resulting amino-azo" dye is diazotised and coupled with the second 'azo coupler.

3. One mol of a 'para-acylamino"diazonom pound is coupled with-one moi-ct a 'sul-fohated'- N-acylaminonaphthol. The acylgroup which was introduced into the 'amino 'd'iaco compound is removed by hydrolysis, and the resulting amino azo dye is diazotised and coupled with one mol of a second azo coupler.

4. The amino azo dye used as intermediate in the methods 2 and 3 can be prepared by coupling one mol of a para-nitro diazo compound with one by reduction of the resulting azo dye.

The first and second methods are suitable only in special cases; the third and fourth methods are of general applicability.

In many cases it is preferable to change the sequence of couplings, that is, to prepare first the amino azo dye containing a suitable azo coupler residue and to couple this monoazo dyewith one mol of a sulfonated Nacylaminonaphtho1. In

fonated N-acylaminonaphthol with a sulfonated aminonaphthol which is coupled in alkaline solution. In this case the resulting diazo dye is acylated by :the action of a suitable acid chloride or anhydride.

Among the diazo or tetrazo compounds suitable for use in the production of the dye which we propose to use, we may mention those obtained from the following amines:

1,4-phenylenediamine -nitro -2-amino-p'-xy1ene 2,6-dichloro-4-nitraniline 3-bromo-5-nitro-2aminotoluene 4-acetylaminoaniline-2-sulfonic acid 4-nitraniline-2-diethylsulfonamide 5-nitro-2-aminobenzylsulfonic acid 1,4-naphthylenediamine-2-sulfonic acid 4-nitro-1-naphthylamine.-6esulfonic acid 5-nitroanthranilic acid Ethyl- (5-nitro-2-aminophenyl) -sulfone 4-acetylamino-5-methoxyaniline-2-sulfonic acid 2-benzyloxy-5-chloro-4-nitraniline 4-nitrani1ine-2-oxyacetic acid, its esters such as the n-butyl, benzyL- cholesteryl and triethylene glycol esters, and its amides such as the N -ethyl anilide and ,N-(4'-nitraniline-2-oxyacetyl) carbazole-,3,6-disulfonic acid 2,5-dimethoxy-4-nitraniline 4 oxalylamino 2,5 di (2 hydroxyethoxy) aniline, its esters and ethers such as its mono ester with phthalic acid and 4-oxalylamino-2,5- di (9' hydroxy 1',4',7- trisoxa n nonyl) aniline 1 oxalylamino 2 ethoxy- 4 naphthylamine- Caproyl-H-acid Naphthylene-1,5-disu1fo-K-acid Carbonyl-bis -J-acid Adipyl-mono-H-acicl Sebacyl-bis-H-acid (m-Aminobenzenesulfo) -S-acid p-Oxybenzoyl-gamma-acid Phthalyl-RR-acid 5-chloronicotinyl-K-acid mol of asulfonated 'N-acylaminonaphthcl and These acylated aminonaphthol sulfonic acids may be replaced by other components, which are obtained by reacting aminonaphthol sulfcnic acids with compounds such as cyanuric chloride, methyldichloropyrimidine, av-dichloroquinoline, 1,4-dichlorophthalazine, dichlorobenzguanamide and 2-chloroquinoxaline-fi-carbochloride. The compound 2,4-dianilino-6-N-(l'-amino-3,6-di sulfo-8'-naphthol)-l,3,5-triazine is a suitable coupling component within the scope of the present invention. The term acyl residue in the appended claims, therefore, has to be understood other cases it is convenient to replace the sulto comprise the residues of organic acidic substances which, when bound to the nitrogen of an aminonaphthol, are regarded in the art of dye chemistry as equivalents for the residues of carboxylic or sulfonic acids.

Those acid radicals containing reactive groups can be reacted further. Sometimes it is necessary to protect reactive groups in the acid radicals of the first azo coupling component for the time of the second coupling or to reverse the sequence of coupling operations, e. g., the (m-aminobenzenesulfo) -S-acid, mentioned above, can be used only in a reversed coupling sequence or after suitable protection of the amino group.

The acylated derivatives of aminonaphthol monoand disulfonic acids, described as firstazo coupling components, may be used as second azo coupling components as well. This leads to a group of azo dyes which are particularly valuable and which have the general formula where both of the acylaminonaphtholsulfonic acid residues may be identical or not.

Other suitable second azo coupling components are the (non-acylated) aminonaphthol monoand disulfonic acids themselves and their N-alkyl and N-aryl derivatives such as ethyl-H-acid, benzyl-H-acid and phenyl-J-acid, which are capable of coupling with diazo compounds in ortho position to the OH group. Among further azo coupling components suitable for the second coupling we may mention the following:

' Those azo' dyes containing a polyfunctional middle component, e. g., ethyleneglycol-bis[2(or 5)-amino-5(or 2)nitro-4-ethoxy phenylJ-ether and/or one or two polyfunctional azo coupling components, e. g., sebacyl-bis-H-acid, are dyes of high molecular weight containing the dye unit several times in their molecule. The general formula for this group of dyes is OH I eae asec x'llhapreferred: method -.of preparation-dbl: dyes .of,.:thisv group. is to produce 'first-monomerlctrs 'yes having reactive terminal groups, e.; g'., amatminot-v .i: group in',.the=-,.acyl residue flinked; towthewamino :naphtholsulfonic acid and/crintheimiddlacom- .rponent,iB-,;land/orr;in';,the second sazo coupling component A'., :oriothenreactive:;terniinalcgroups suclriasicarboxyl .:0r. alcoholic. or; ethylene: groups sinranywonetioflthesez nuclei. ;-lI-'he;finish.ed :iimqno- :meric-:adisazo' :dye; is: treated ,with suitable: re-

agents such as phosgene to produce external linkages. Suitable external linnkages' are: CO--.-. -CS, CX2 (where X is hydrogen, alkyl or aryl) SO2, S-, NX-, (where R is a bivalent hydrocarbon: residue), -NHCONH-, NHCSNH- like. Some of these linkages suchas SO zare preferably present in thestartingmat'erials from which the dyes are prepared, whereas other linkages u h. as --NHCO"NH-"are"intro-30 a nm duced into monomeric dyes in theaboveidescribedmanner. These methods are disclosed inl'detail' in U. S. Patent No. 2,470,769. I

By way of example, but not in'limitationiithe some of the processes for obtaining the same.

is prepared in the following way: 4-'-nitro'--l napthylamine-B-sulfonic acid is.diazotisedand a somewhat less greenish blue-green dye.

coupled with toluenesulfo-I-I-acid. The --a zodyle,

thus obtained is dissolved in an excess of sodium hydroxide and stirred at 60 C. with sodium su1-' fide, until the color of the solution, which isviolet blue at the beginning turns orange. Thereupon o the chemical character. oi thesubstrate; e,..g., a

the solution is buffered with sodium bicarbonate, the intermediate. dye. is precipitated bythe addition of sodiumchloride, isolated by filtration and washed. Thefiazo dye is dia'zotized in known manner-and the chemo solution is addedat 5 C. to, a stirred solution of toluenesulfo H acid fin aqueouspyridine. After'three hours, these-lution "is acidified and; precipitated with'jsodi'um "chloride." :By-washing,"'with sodiumchloride'solw tion .01. by liepleclpitating withjjsodiuml chloride 6 1 'from the aqueous solutionthe' .dye' is freed-item purple impurities.

l is prepared by coupling 2-amino-5 -nitro- .eilheglye is quite soluble in'watertand -d-yes wool iandcsilk n= blue, green shades. rmdry gelatinfilm, t ining'thisdreams;a sharpmaximum oI ab- ;sorption a-t'about fififl mu. g

. nam

r ydroquinonedimethyli ether; with "acetyleH-acid,

reducing the dye thus obtained and by cou- ,.-p1ing{the' intermediatei dye with sulfophenylpyrzaaolonecarbonic acid -I ('tartrazinogenie sulfonlc 'a ilDyes 20f "rained if the middle.component is replaced by dioxyacetio acid di-ethyIether .e-H-Jacid isreplaced by (3-acetylr: orl l'ii the jaeetyi arninebenz'enesifliolfl-lsacid. Furthermore, 1.0116

imoli'bf the tartrazinogenic acid in the above ex- 7 l following illustrate specifically our new dyes and can be rep aced by one half mol of H V .acyl-K-acid instead of the acetyl H-acid, have of 1ith ese components with acetyl-J-acidyields ,"TI lhose'dyes containing a second azo coupler free-from solubilizing groups are in most cases difficulty soluble in water. The color of the dyeings with these difficulty soluble dyes depends on ihefi average urrioledtilarxweight of 14000) Site the 'igelatin. s

t Emmp1e3 1 v 12 ml. of a 2% solution of the dye'i' :lOCaHs gen nufieo cn l pinz practically ethe same shade areiob- J I are a ded-15010 m1- f red-s nsi i ed "silver from 1,8 aminonaphthol such as H and K acids. broniide emulsion. This] emulsion e'ce'ateuwn At least one of such coupling components is a support; and the coating is used for; the bottom acylated by a carboxylic or sulfonic acid at the layer of 'amultilayer material." The material is amino group, those acylated. with a carboxylic eXpOSed and developed n k a e '5 acid being preferable. The dyes of this group dye is destroyed at the'places'where metallic have excellent spectralcharacteristics and do silver is present, e. g., in a hydrobromic acidbath not diffuse or desensitize a" photographic emulcontaining 2,3-dimethylquinoxaline, the'metallic sion; and furthermore, give colorless reduction silver is oxidized in a copper chloride solution products in dye bleaching processes of' color and removed in a hypo bath. Aifter this treatlo-photography. V

merit the bottom layer ofthe material contains Since from the foregoing description of the a positive brilliant cyan image of excellent light invention it will be apparent to those skilled in fastness and definition. Amicrotome section re- .the art that many variations of this invention veals that no cyan dye has diffused into the may be made without departing from the spirit ne ghbonng layers, and scope thereof, it is to be understood that we Further examples are arranged 1n the follow do not limit ourselves to the specific examples mg table: thereof except as defined in the appended claims.

No. AN=N- -B N=N A -Ool0r I 8-p -toIuenesulfonylam inol,4-phcnyleuec 8 -p-toluenesulionylsmi11oblue.

' 1 hydroxy 3,6 disulfo- 1 -hydroxy 3,6 clisulio' naphthalene-2-azo. V v naphthalene-2-azo. 2. do v do 8 amino-l hydroxy fi-sulio- Do,

I naphthalene-H20. 3... ..do do.. -6'- amino 1 hydroxy 3-- Do.

- v sl'llfo 5 (2,5-diehloro- I phenyl-azo) naphthalene- Z-azo. 4.-. do 2,6-dichIoro-1AE '8p-toluenesulfonyl-aminoblue-violet,

- I v phenylene. 1- hydroxy 3,6 disulfo- 1 naphthale11e-2 azo'. 5. 1,4-phenylene- 2 do blue-green.

. oxyaceti'c acid. v.6... 2,5 dimethoxy l hydroxy 8 -'ch1oro 3,6 Do.

1,4 phenylene'. disulfonaphthalenefieazo. 7--. I -.'-;do 2-hydroxy-naphthalene-1- Do azo. 8.-. 1 methyl 2,4 dioxo -1,2,3,- Do.

4 tetrahydro quinoline 3 9--. acetoacetio chloroanilide Do.

' beta-azo. 10.. S-ecetylamino-l -hydroxy- S-benzoylamlno-l-hydroxy- Do.

5 sulionaphthalene 2 phenyl-i-azo. azo. 11-. .do 1 phenyl 3 methyl 5 Do.

. pyrazoloue--azo. 12-- do 1 :1 hydroxy naphthalene Do.

- -az0. 13-. do B-acetylamino-l -hydroxy- Do.

5 sulionaphthalene 2 azo. 14-- ..do 6 anilino l hydroxy 3 Do.

sulfonaphthalene-Z-azo. 15-. do 7- (2- amino -ethy1)-amino- Do.

1 hydroxy 3 sulfonaphthalcne-Z-azo. 16.. do. 2 hydroxy 3,6 disulfo- Do.

naphthalene-Lam. 17.- 6acetylamino-1-hydroxy- V 6-acetylamino-1 -hydroxy- Do.

naphthalene 3 -sulfo 2- '1 3 sulfonaphthclene 2 azo. .t azo. l 18 do Lido; 8-amino-l-hydroxy-5J- Du.

- y disulfonaphthalene- 2-820. 19.. l do ..do S-amino -1 -hydroxy-3- Do.

' sulfo nephthalene- 2 azo.

he blue and blue-grerlfdyes, described and We claim:

exemplified above, have an unusual brilliancy. v 1. A bluish azo dye of thegeneral formula" Their fastness to light depends mainly on the I OH OH acylresidue'attached to the aminonaphthol sul- A B A, M1

ionic acid. Whereas, e. g., the fastness of the co dye obtained. by coupling vtetrazohyclroquinone wherein B is an aromatic nucleus in which the dimethyl ether with toluenesulfo-H-acid, is not azo bonds shown stand in 1,4 posiitbn, A and sufficient for all puiposesQthe dye'obtained by are naphthalene nuclei, the y yl groups coupling tetrazohydroquinone dimethyl ether shQWn Standing in Ortho position 'to the azo with 2,4-dichlorobenzoyl-H-acid has excellent groups Shown at least one of said phthalene fastness to light-h 1 nuclei A and A carrying from lto 2 -,-SO: cation The dyes preferred in accordance with the g V invention are those containing ether groups in Y in g g ggg g g mlacccFdance With claim 1 the central portion (-B) of the molecule, boxync acid mm 232 3 radicals shown are especially those containing 1 ether grqupsin" 3. A bluish azo dye irfsccordance with l para posltlon- 1 l in which each of the acyl radicals shegvg' gr The preferred coupling components are,the ulfo i acid acyl'mdica e aminonaphthol sulfonic acids containing 1 or 2' v .4. A bluish azo dye in accordan e t claim 1 sulfonic acid groups, particularly those derived in which B is a, benzene 11 1 5. A bluish azo dye in accordance with claim 1 I in which B is a benzene nucleus carrying at least one ether radical in at least one of the positions two and four of the benzene nucleus in which the ether oxygen is bound directly to the ben- 5 zene nucleus.

6. A bluish azo dye of the general formula wherein B is a benzene nucleus in which the azo groups shown stand in 1,4 posiiton, and wherein at least one of the naphthalene nuclei shown carries from 1 to 2 --SO:; cation radicals.

'7. A bluish azo dye in accordance with claim 6 in which B is a benzene nucleus carrying at least one ether radical in atleast one of the positions 2 and 4 of the benzene nucleus in which the ether oxygen is bound directly to the benzene nucleus.

8. An azo dye of the formula GOO-NH on ?C2H5 BELA GASPAR; 7 PAUL DANIEL DREYFUSS.

REFERENCES CITED The following references are of record in the file of this patentr UNITED STATES PATENTS Number Name Date 546,068 Krecke et al Sept. 10, 1895 1,101,739 Gunther et al June 30, 1914 1,150,675 Gunther et a1 Aug. 17, 1915 1,663,950 Neelmeier et al. Mar. 27, 1928 1,699,427 Fellmer Jan. 15, 1929 2,125,625 Delfs et a1. Aug. 2, 1938 2,424,066 Straub et a1 July 15, 1947 FOREIGN PATENTS Number Country Date 14,576 Great Britain 1902 8,569 Great Britain 1914 514,353 Great Britain 1939 107,228 Sweden Apr. 27, 1943 OTHER REFERENCES Cain et al.: SyntheticDyestuffs, 6th edition, 1923, page 57. 

8. AN AZO DYE OF THE FORMULA 